Metal working lubricant



Patented Dec. 9, 1952 {UNITED STATES PATENT Calif., 'assignorsto Shell. Development Com- 'pany,-. San Francisco, Calif; a 1 corporation of Delaware NoDrawing. *ApplicationNovember 5,1949, Serial No. 125,839

Thisinvention relates to novel'lubricants and methods of :making themJ'More particularly; this --inventionpertains to metal working or'rmetalfabrication lubricants" for' use in rolling, drawing,

p drawing; rod and tube i'drawing, :forging of metals and th like.

' Problems '1 encountered :in lubricating. metals under: conditions of the .usesl referred to in the previous paragraph are particularly complex because of the. various factors encountered, such as high temperature, excess pressure, emulsificatiompresence of foreign bodies or contaminants, work speeds and the like. To eifectively lubricate under these adverse :conditions, the

lubricantamust act" primarily 1 as a coolant and i l as a lubricant.

In the afield of rolling lubricants'palm oil has been considered to be .most- 'efiicient and 1 suitable for .use' in connection 'with the heavier: metals such as iron and itsalloys, steels. "However, palm ers,='which'igreatlyincreases operating cost. .Also,

it hasna tendency to stain some metalsuriaces which on annealing mars the surface andexerts a detrimental efiect when such *metalsz are to be subsequently tinned/coated and the like. :In addition, metal surfaces which become too heavily: coated: with palm oil-cause excessive slippage of the. rolls thereby decreasing. rolling: efiiciency. :Palm oil is not always'readilyiavailable;

hence acheap andefiective substitute 'for'it is greatly .desired.

To meet the requirements demanded of: ajgood metal-fabricating lubricant, such: as a roll lubricant, it must. have as: essential properties film strength. ability to. reduce friction, "ability :to wet metals in presence= of *waterpability to pro duce a good lustreon metalisurfacerworkedyease of re- 40 metal -:and non-staining and ric-emulsifying properties, i.- e.,'-separating from water and contaminants, including fines.

7 .FILM' STRENGTH When lubricated metal surfaces areforced to slide past each'other under high pressures, there is a tendency for surface asperitiesto penetrate the lubricant film and the penetrating metal to adhere to the opposingmetal surface; this permits the transfer of metal from one surface to another. This phenomenon, known in metalworking operation as pick-up of the worked metal by the die or roll, may become very pronounced at elevated temperatures. Although high temperatures may be a result of high friction and may lead to pick-up," it is generally agreed that the ability of a lubricant to prevent adhesion of metal surfaces is a property distinct from and notnecessarily related to ability" of the :12 lubricant to reduce friction between sliding-stir faces which do I not adhere. iFor -this" reasong the ability eta-lubricant to form surfacefilmsltvhich prevent actual KmetaPto-metaI" contact I and: ad-

5 :hesion is veryl essential.

- REDUCTION OFFRLICTION 'iRoll lubricants must :pos's'ess the-'- ability to reduce friction'between the rolls and theiworksheet p in .order to "reduce; power consumption, increase reduction per-pass: andzgive 'a lower limit toethe metal thickness,; prevent, overheating 'andiminimize the force which must be appliedrto the rolls. -Thegproperty of a lubricant'to reduce friction is 15 referred to 'looselywas oiliness and dependsiupon oil has serious drawbacks, particularly in some :applicationain' that it isdifiicult to'remove from metal surfaces thereby requirin the use of cleanthe sheer strengthiof the .film formed on ametal surface and to the rheological behavior of thin films of oilwhen" subjected to-highpre'ssures.

WETABILITY' AND ADHESION Sincerolllubricantsare usually used-in icon- -junction with water as. acoolant, theymust possessthe property of displacing water from metal surfaces and resistthe 4 washing action. ofwlarge quantities of water applied-t0 the rolls-andwofl; sheet. Often washing water :is applie'd in the form of a high pressure stream so that the ability of the lubricant to adhere-tometal-surfaces issof paramount importance.

LUSTRE Theappearance ofthe. surface of rolled-stock referred to in practice as lustreis markedly influenced by the character of the rolllubricant.

3? To accomplish this, lubricants'used for thisjpurpose should prevent microscopic tears on the worked metal surface.

EASE 'OF *R'EMOVALA'NDNON-STAIN1NG CORROSION RESISTANT Efficient roll lubricants in' addition to fb'ein'g able to withstand high temperature and pressure must be non-corrosive during the rollirigprocess and preferably actas a corrosion inhibitor after no the rolling processfparticularly in"cases"where 3 the rolled metal is stored for'long intervals before being further worked.

It is an object of this invention to provide an improved metal-rolling lubricant. It is another object of this invention to provide a lubricant for metal working which is stable and non-corrosive. Still another object of this invention is to provide a tacky metal-working lubricant havin the property of resisting water displacement from metal surfaces. Furthermore, it is an object to provide a metal-working lubricant which is non-staining and which can be easily removed from lubricated surfaces. A more specific object is to provide an improved lubricant for use in the working of aluminum, stainless steel and other metals and alloys.

It has now been discovered that a metal-working lubricant such as a rolling lubricant having outstanding properties can be prepared by forming a blend of a waxy hydrocarbon, substantially non-aromatic and a polymeric olefin, waxy hydrocarbon comprising at least 80% and preferably 85 to 95% of the blend, said blend having admixed therein as a primary ingredient from about 3% to about and preferably from about 3% to 6 of a halo-organic compound such as halo waxes, halo-fatty acids and esters thereof and the like.

Waxy materials can be recovered from residuum lube oil fractions, and these wax fractions can be split still further into special wax cuts having desired characteristics by use of selective solvents. This is based on a difi'erence in solubility of different waxy fractions in a given solvent. Thus, when using a methylethyl ketone type solvent, the aromatic constituents can be removed by successively cooling the mixture down to between about 40 F. and 76 F. so as to remove the aromatics which remain substantially soluble in the solvent as the temperature is lowered, while the straight-chain waxes and isoparafiins become substantially insoluble in the solvent. The straight-chain Waxes can be separated from the isoparaffins by extraction and fractional crystallization.

The above type of waxy hydrocarbons may be admixed with synthetic waxes produced by polymerization of olefins under pressure or by dehydrating long-chain fatty alcohols such as octadecyl alcohol and the like. Admixed with nonaromatic waxy hydrocarbon may be minor amounts of Waxy materials obtained from nonhydrocarbon services such as marine or animal waxes, vegetable waxes and the like, and specifically may be illustrated by spermaceti, Japan wax, carnauba wax, montan wax, sugar cane wax. cotton wax, etc., and the mixture oxidized.

The other constituent of the base blend is a polymeric unsaturated hydrocarbon and may be monoand/or polyolefinic and/or acetylenic hydrocarbons, which may, if desired, have attached polar groups, said polymeric materials being of rather high molecular weight such as above 300 and preferably above 1,500 and may even be within the limits of 5,000 or 10,000 or even higher, such as 100,000 or 500,000, etc.

These olefinic products may be obtained from various sources and by various means. Thus, olefins may be obtained by hydrogenation of parafiins, such as by the cracking of paraffin waxes, or by the dehalogenation of alkyl halides and the like. Also, as olefinic starting materials for the production of such polymers, individual olefins or mixtures of olefins and non-olefinic hydrocarbons may be used. Starting materials may Y be butylenes, amylenes, refinery gases containing normally gaseous olefins and cracked distillates or other relatively low-boiling hydrocarbon mixtures containing normally liquid olefins, and mixtures of normally liquid olefins containing dissolved therein normally gaseous olefins. Polymers resulting from the treatment of monoolefins preferably iso-monoolefins such as isobutylene and isoamylene and/or copolymers obtained by the polymerization of hydrocarbon mixtures such as isoolefins and normal olefins may be used. The polymerization of these olefins and their mixtures may be obtained by use of suitable catalysts such as Friedel-Crafts type and the like.

Examples of olefinic and/or acetylinic hydrocarbons which may be obtained from any source and utilized in forming the desired sulfurized products of this invention are ethylene, propylene, butene-l, butene-2, isobutylene, the amylele, hexene-l, 4-methyl-pentene-1, 4,4-dimethylpentene-l, 4-methyl-pentene-2, octene-l, decene-l, cetene-l, styrene, cyclohexene, 3-methylcyclohexene, 1,4-diphenyl, butene-2, butadiene 1,3, pentadiene-1,3, pentadiene-L4, hexadiene- 1,5, hexadiene-1,4, pentadecene-8, heptadecene, hexadecene-l, tridecene-7, nonadecene-lO, 3,9- diethyltridecene-6, dodecene-l, triacontene-14, pentatriacontene-l'l, olefins, obtained by decarbonylation of oleyl alcohol or such unsaturated alcohols as are obtained by carboxyl reduction of sperm alcohol, olefins obtained by dehydration of high molecular weight saturated alcohols, etc., acetylene, propyne, butyne-l, pentyne-Z, hexyne- 1, cetyne-l, octyl acetylene, phenyl acetylene, etc, and their homologues and analogues.

Copolymers of olefins and non-aromatic hydrocarbons may also be used. The olefins which may be used to form the copolymers of this type include isobutylene, 2-methylbutene-1,2, ethylbutene-l, secondary and tertiary amylenes, hexylenes and the like. The non-aromatic hydrocarbons may include butadiene, isoprene, cyclopentadiene, 2,3-dimethylbutadiene-1,3, pentadiene-1,3, hexadiene-2,4, the substituted di- -olefins such as diisobutenyl; the acetylenes such as acetylene, vinyl acetylene and the like.

The copolymerization is preferably carried out in the presence of a Friedel-Crafts type catalyst and in the presence of a suitable diluent such as liquified ethylene, propane and the like.

- The catalysts which may be employed during the polymerization reaction may be any Friedel- Crafts catalyst such as are listed by Galloway in Chemical Review 17, 327 (1925). The polymerization may be carried out at low temperatures such as below zero degrees centigrade, or at elevated temperatures such as above 50 C. and C. and higher.

Among the most preferred polymeric materials suitable for use in compositions of this invention are:

Polyisobutylene polymer (mol. wt. 1,5005,000) Polyethylene polymer (mol. wt. LOGO-10,000) Polybutenes (mol. Wt. 5,000-6,000)

Copolymer of isobutylene and ethylene (mol. wt.

Copolymer of propylene and wt. EGO-10,000)

Copolymer of butadiene and wt. l5,000-20,000)

isobutylene (mol.

isobutylene (mol.

wax: o'lcflns, halogenated fatty acids having at least 8 and preferably 12 to 24. carbon. atoms in the molecule, esters of said fatty acids-and the like. The halo radical or radicals maybe: chlo' rine, bromine, fluorine, and/01s iodine. Agents which. are specifically preferred arechlorinated parafiin wax, chlorinated cracked wax, chlorinated foots oil, olefin of Clo-C24,. chlorinated synthetic rubber, chloro-bromo-parafiin wax, dichlorostearic acid, dichloro-oleic acid, methyl dichloro-stearate, butyl dichloro-stearate, polybromostearic acid, methyl polybromostearic acid, methyl dichloro-ricinoleate, chlorinated. waxy esters, e. g., beeswax, montan wax, and the like.

Highly desirable metal-working lubricants such as rolling and drawing lubricants can be prepared by using formulations within the following range Material Amount Base blend; Berce nt v l. Waxy-hydrocarbon t 804) 1 2. Polymeric material mol. wt. 30050D,000 and p 97 89 prefrably'l,500-5,000 20-5" PrimaryAdditive:

3. Halo-organic compound, e. g,',. chlorinated paraflin' wax or methyldichloro-st'earate', etc. 2-l0" Secondary or optional Additives:

4; Amines,.sul.fonates, etc (H.

Specific compositions. of this invention: are:

C (imposition .4

Per. cent Methyl. dichlorostearate .u 3 Polybutene' (mol.. wt. 8,000-l0,000)f I0;

Soft Wax residue (M. P. 39"'-4=0'- C.) Balance:

Composition C Per cent Dichlorostearic acid Polyisobutylene (mol. wt. -l,50010,000) 5 Residue petrolatum Balance Composition E Per cent Methyl dichlorostearate 3 Sulfurized sperm oil 1 Polyisobutylene 5 Soft wax obtained from residue petrolatum (M. P. 40 C.) Balance Composition F Per cent Chlorinated parafiin wax Polybutene (mol. wt. 8,000-10,000) 5-10 Residue petrolatum Balance Table I below further illustrates compositions of this invention:

Table I petrolatum residual wax 2: :r z (b) polymeric materialpolyethylene Z polybutene a: :r

30C. C C:

Composition D' p D 1 D p otir bsinoirnz 5 .10 2042 .69 .045- GompcsitionF .65: 1.0411 -67 .1140 GompositionX 2.1 .16 Composition Y" 1.5 .101 GompositioIlZZL c E 2.2 2.25.

D=S C3l'fdialneter;. mm; =Coefi. of friction, average of values at 30, 40, 50 and 60scconds'a =seizure v Compsitlon2X=10%polybutanem residuepetrolatunr.

4 Composition =10%; olei'c; acid+ 3% chlorinatedparaflin wax-i in p'a'rafiim wax;

Composition Z=1% tricresyl phosphate in mineralloilz In conjunction with compositions of this in.-

-' vention, minor amounts, generally less than- 1%,

of other additives can be added, if desired, in order to fortify the compositions, such as:

A. High molecular weight; fatty acids derived.

7 4 from-animal, vegetable, marine oils,-.e. g-.,

1. Animal o'il:

tallow neats foot lard wool fat bone horse foot oils, etc.. 2.- Vegetable oils:

castor corn cashew" cottonseed" peanut kapok. cocoanut rapeseed ioiobaseed ravison olive sesame; olive kernel sunflower palm oil teaseed oils;.'et'c'.v palm kernel oils 3. Marine oils:

codfish porpoise body and jaw oils codliver salmon oil dogfish sardine and sardine liver oils dolphin body seal oil dolphin fish shark and shark liver oils herring sperm whale body and head oils 1apfish whale 011, etc. menhaden B. Natural-occurring fatty acids of high molecular weights:

1. Saturated:

capric stearic undecylic arachidic lauric lignoceric myristic cerotic palmitic montanic acids, etc. 2 Unsaturated A oleic linolenic linoleic brassidic erucic elaidic acids, etc. 3. Substituted fatty acids:

ricinoleie ricinelaidic stearate, di-2-ethyl hexyl-azelate, n-decyl hydrogen phthalite or succinate, octadecyl stearate.

2. Esters of inorganic acids, e. g., phosphatidic materials such as cephalin and lecithin.

D. Sulfur-containing materials, e. g.,

sulfurized sperm oil sulfurized cottonseed oil sulfurized fatty acids as listed under part B Rolling lubricants of this invention are well adapted as rust inhibitors after the rolled sheet has been worked.

The roll lubricant of this invention may be applied to the rolls of a sheet metal rolling mill by any suitable means such as spraying. dripping, or the like. It may be applied to the sheet metal prior to or during rolling.

In addition to being an excellent roll lubricant, compositions of this invention may be used as drawing lubricants, forging and die lubricants and in various other processes where drawing m z-an10 of mammal used and can be e ranges 75 and working of metals requires lubrication.

disclosed in column 5.

It is to be understood that while the features of the invention have been described and illustrated in connection with certain specific examples, the invention, however, is not to be limited thereto or otherwise restricted except by the prior art and the scope of the appended claims.

The invention claimed is:

1. A metal-working lubricant consisting essentially of a base blend of a soft residue wax and an olefinic hydrocarbon polymer having a molecular weight above 300, said soft residue wax constituting at least 80% of the blend and the polymer constituting essentially the remainder of said blend, and having incorporated in said base blend from 2% to 10% based on the total lubricant, of a halogenated extreme pressure compound selected from the group consisting of halogenated wave, halogenated high molecular weight fatty acids, and hologenated esters of said fatty acids.

2. A metal-working lubricant consisting essentially of the following components in the specified proportions:

Per cent Methyl dichlorostearate 3 25 Polybutene (mol. wt. 8,000-10,000) 10 Solt wax residue (M. P. 3940 C.) Balance 3. A metal-working lubricant consisting essentially of the following components in the specified n proportions:

Per cent Chlorinated paraflin wax (40% C1.) 3 Polybutene (mol. wt. 8,000-10,000) 5-10 Soft residue wax Balance 4. A metal-working lubricant consisting essen tially of the following components in the specifled proportions:

Per cent Methyl dichlorostearic acid 3 Oleic acid l Polyisobutylene 5 Soft residue wax Balance 5. A metal working lubricant consisting essentially of the following components in the specified proportions:

I Per cent Methyl dichlorostearate' 3 Sulfurized sperm oil 1 Polyisobutylene 5 Soft residue wax Balance GEORGE L. PERRY. SAMUEL K. TALLEY.

REFERENCES CITED The following references are of record in the OTHER REFERENCES Lubrication as Affected by Physical Properties of Lubricants, Williams, January 1935, Industrial and Engineering Chemistry, vol. 27, No. 1, PD. 64 and 65. 

1. A METAL-WORKING LUBRICANT CONSISTING ESSENTIALLY OF A BASE BLEND OF A SOFT RESIDUE WAX AND AN OLEFINIC HYDROCARBON POLYMER HAVING A MOLECULAR WEIGHT ABOVE 300, AND SOFT RESIDUE WAX CONSTITUTING AT LEAST 80% OF THE BLEND AND THE POLYMER CONSTITUTING ESSENTIALLY THE REMAINDER OF SAID BLEND, AND HAVING INCORPORATED IN SAID BASE BLEND FROM 2% TO 10% BASED ON THE TOTAL LUBRICANT, OF A HALOGENATED EXTREME PRESSURE COMPOUND SELECTED FROM THE GROUP CONSISTING OF HALOGENATED WAVE, HALOGENATED HIGH MOLECULAR WEIGHT FATTY ACIDS, AND HOLOGENATED ESTERS OF SAID FATTY ACIDS. 